MERZ, A and BACHMANN, H (1995) OLIGO(ETHYLENE GLYCOL)-SPACERED SILOXANE REDOX POLYMERS - HIGHLY DIFFUSIVE MEDIA FOR ELECTROCHEMICAL REDOX CATALYSIS. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 117 (3). pp. 901-908. ISSN 0002-7863,
Full text not available from this repository.Abstract
Redox-modified oligosiloxanes were prepared from an Si-60 oligo(hydrogen siloxane) and allyl-terminated oligo(ethyleneglycol) (OEG) esters of 3-carboxy-2,2,5,5-tetramethyl-Delta 3-pyrroline-1-oxyl (PROXYL-COOH). Glassy carbon disk electrodes coated with the modified siloxane films were obtained by spin coating with film thicknesses between 10 nm and 15 mu m and analyzed by cyclic voltammetry, chronoamperometry, and rotating disk voltammetry in acetonitrile and water. Due to the OEG content, the siloxane matrix offers a high. diffusivity with respect to the mobility of redox centers and solute species. The PROXYL-mediated catalysis of the oxidation of 4-methoxybenzyl alcohol (PMBOH) to anisaldehyde was studied at spin-coated glassy carbon disk electrodes by cyclic voltammetry in acetonitrile with lutidine as a base and in buffered aqueous solution at pH = 7. The catalytic efficiency is 10-fold higher in the latter medium. In controlled potential microelectrolyses, current densities up to 15 mA/cm(2) and catalyst turnovers up to 30 000 were determined at ca. 0.1 mmol/cm(2) substrate conversion. Crucial factors of film performance are thickness and homogeneity, which are still difficult to control at larger area carbon felt electrodes.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CHEMICALLY MODIFIED ELECTRODES; CHARGE TRANSPORT; KINETICS; OXIDATION; FILMS; COMPLEXES; REDUCTION; FERROCENE; MECHANISM; STATE; |
| Depositing User: | Dr. Gernot Deinzer |
| Last Modified: | 19 Oct 2022 08:38 |
| URI: | https://pred.uni-regensburg.de/id/eprint/52789 |
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